WO2011093508A1

WO2011093508A1 - Polyalkylene glycol derivative and cosmetic comprising same

Info

Publication number: WO2011093508A1
Application number: PCT/JP2011/052028
Authority: WO
Inventors: 洋二手塚; 恵介石川; 和晃脇田; 圭一円山; 哲志阿部; 佑介青木
Original assignee: 日油株式会社
Priority date: 2010-02-01
Filing date: 2011-02-01
Publication date: 2011-08-04
Also published as: KR20120112705A; KR101772720B1; CN102741322A; CN102741322B

Abstract

Provided is a novel polyalkylene glycol derivative represented by general formula (1) which exhibits an excellent performance as a surfactant. In formula (1), EO represents an oxyethylene group; AO represents a C3-4 oxyalkylene group, provided that EO and AO are bonded in a block form; a and b represent the average number of EO moles added and m represents the average number of AO moles added, provided that a+b is 0-100, m is 10-100, and the ratio by mass of (AO)m to the total mass of (EO)a, (EO)b and (AO)m is 50-100 mass%; and R1 represents a hydrogen atom, a C1-4 alkyl group or a C1-4 acyl group.

Description

Polyalkylene glycol derivative and cosmetic comprising the same

The present invention relates to a polyalkylene glycol derivative suitable for a nonionic surfactant and a cosmetic comprising the same.

Surfactant has the effect of adsorbing to the interface, lowering the interface energy, and thermodynamically stabilizing the system. In general, the structure has both hydrophilic and lipophilic groups in the molecule, and it is mainly used as an emulsifying solubilizer at the liquid-liquid interface, and it has various properties such as dispersion of particles and improved wettability at the solid-liquid interface. Demonstrate the characteristics.

Among surfactants, nonionic surfactants, along with anionic surfactants such as soap, are indispensable to industry, and have a low critical micelle concentration and can be used at low concentrations. Widely used in the field.

Particularly in the cosmetics field, various oils such as hydrocarbon oils such as liquid paraffin and squalane, fats and oils such as vegetable oils and triglycerides, ester oils having ester bonds, and silicone oils such as dimethylsiloxane are stably blended in the presence of water. There is a need. Furthermore, in order to protect the skin from external factors such as ultraviolet rays, it is also necessary to ensure the dispersion stability of inorganic powders such as titanium oxide and zinc oxide.
Thus, a nonionic surfactant that works effectively at the liquid-liquid interface and the solid-liquid interface is indispensable.

Focusing on conventionally used nonionic surface active lipophilic groups, many of them are long-chain alkyl alcohols derived from animal and vegetable fats and oils or synthetic alcohols based on them (for example, Patent Documents 1 and 2). Industrially, only a molecular weight of about several hundreds was obtained, and it was difficult to exhibit sufficient lipophilicity.

On the other hand, a hydrophilic group is known to act as an adsorptive group to the solid surface at a solid-liquid interface in which a solid such as a metal oxide is dispersed in a liquid. However, there was a problem in adsorption capacity compared with the hydroxyl group. In addition, sorbitan fatty acid esters, polyglycerin fatty acid esters or ethers (for example, Patent Documents 2 and 3) that are widely used industrially have a hydroxyl group derived from a polyhydric alcohol as a hydrophilic group. The molecular weight of the group was limited, and there was a problem in exhibiting sufficient effects.

In order to solve such a problem, a surfactant in which oxybutylene group is introduced as a lipophilic group and polyglycerin is introduced as a hydrophilic group has been proposed (for example, Patent Documents 4 and 5). However, even in this proposal, although the surface activity ability to the liquid-liquid interface is excellent, since the hydroxyl groups serving as the adsorption sites are at both ends, the interaction between the hydroxyl groups is poor, so the adsorption ability to the solid surface is poor. As a result, a sufficient effect was not obtained with respect to the surface activity at the solid-liquid interface.

Japanese Patent Laid-Open No. 10-212491 Japanese Patent Laid-Open No. 2003-213036 JP 60-28944 A JP 2007-31554 A JP 2008-188557 A

An object of the present invention is to provide a novel polyalkylene glycol derivative exhibiting excellent surface activity and a cosmetic having long-term blending stability by blending such a novel polyalkylene glycol derivative. That is.

In order to solve such a problem, attention was paid to a polyoxyalkylene group capable of controlling the molecular weight as a lipophilic group of a polyalkylene glycol derivative. Furthermore, as the hydrophilic group, attention was paid to xylitol in which four hydroxyl groups having excellent adsorptivity to the solid surface are adjacent. That is, a protecting group is introduced into xylitol, an oxyalkylene group having 2 to 4 carbon atoms is introduced, alkylation or acylation is performed as necessary, and then deprotection is performed to thereby remove four adjacent hydroxyl groups. It was found that the emulsion can be localized and the emulsification solubilization ability and dispersion ability are improved.

That is, the present invention is as follows.
(1) A polyalkylene glycol derivative represented by the following general formula (1)

In the formula, EO is an oxyethylene group, AO is an oxyalkylene group having 3 to 4 carbon atoms, and EO and AO are bonded in a block form. The plurality of AOs may be the same as or different from each other.
a and b are the average addition moles of EO, m is the average addition moles of AO, a + b is 0 to 100, m is 10 to 100, (EO) a and (EO) b The ratio of the mass of (AO) m to the total mass of (AO) m is 50 to 100 mass%.
R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group having 1 to 4 carbon atoms.

(2) The polyalkylene glycol derivative according to (1), wherein AO is an oxybutylene group derived from 1,2-butylene oxide.

(3) In the polyalkylene glycol derivative represented by the formula (1), b = 0, and the ratio of the mass of (AO) m to the total mass of (EO) a and (AO) m is 80 to 100 mass%. The polyalkylene glycol derivative according to (1) or (2).

(4) A cosmetic comprising the polyalkylene glycol derivative according to any one of (1) to (3).

(5) 0.01 to 30% by mass of the following component (a), 0.1 to 50% by mass of component (b), 5 to 80 of component (c), component (d), and component (e) The total amount of the component (c) and the component (d) is 10 to 95% by mass, and the total amount of the component (c) and the component (d) is 100 parts by mass. The cosmetic according to (4), wherein the amount of the component (c) is sometimes 10 parts by mass or more.
(A) Polyalkylene glycol derivative (b) Inorganic pigment (c) Hydrocarbon oil liquid at 25 ° C. (d) Silicone oil (e) Water

The polyalkylene glycol derivative of the present invention exhibits an excellent surface activity, and a cosmetic containing it is also very useful.

It is a graph which shows the light absorbency of 300 nm of the diluted solution of each example.

[Polyalkylene glycol derivatives]
The polyalkylene glycol derivative according to the present invention is represented by the following general formula (1) and has a xylitol skeleton.

In the polyalkylene glycol derivative represented by the formula (1), EO is an oxyethylene group, and AO is an oxyalkylene group having 3 to 4 carbon atoms. Examples of AO include an oxypropylene group having 3 carbon atoms and an oxybutylene group derived from 1,2-butylene oxide, an oxyisobutylene group, an oxyt-butylene group, and an oxytetramethylene group having 4 carbon atoms. , An oxybutylene group derived from 1,2-butylene oxide. When these are two or more kinds, random addition or block addition may be used.

The addition form of EO and AO is block-like, and is added to xylitol in the order of EO-AO-EO ((AO) m is added to the end to which (EO) a is added, and (EO) is added to the end (EO). ) b is added). If EO and AO are added in a random manner, the surface activity cannot be obtained, which is not preferable.

Here, in formula (1), xylitol and EO part act as a hydrophilic group as an emulsifying solubilizer and as an adsorption site as a dispersing agent. On the other hand, the AO part acts as a lipophilic group as an emulsifying solubilizer and as a dispersion site that brings about steric repulsion as a dispersing agent. That is, the polyalkylene glycol derivative represented by the formula (1) can be used as a nonionic surfactant.
m is the average number of moles of AO added. When two or more kinds of AO are present, the total average number of moles added is 10 to 100. In the polyalkylene glycol derivative of the present invention, the AO site acts as a lipophilic group. However, when m is less than 10, the molecular weight is not sufficient as a lipophilic group, and sufficient when used as an emulsifying solubilizer. The effect may not be exhibited, and when used as a dispersant, sufficient steric repulsion cannot be obtained, which is not preferable. From such a viewpoint, m is more preferably 20 or more. On the other hand, if m exceeds 100, a sufficient effect may not be exhibited due to the influence of side reaction products, which is not preferable. From such a viewpoint, m is more preferably 80 or less, more preferably 70 or less, and most preferably 50 or less.

EO can be added as necessary to supplement the hydrophilicity of the xylitol skeleton. a + b is an average added mole number of EO of 0 to 100, preferably 50 or less, more preferably 30 or less. When a + b is larger than 100, the compatibility with the oil agent cannot be sufficiently obtained, and a sufficient effect cannot be obtained when used as an emulsifying solubilizer, which is not preferable.

In the case of a = b = 0, the polyalkylene glycol derivative of the present invention has only a xylitol site as a hydrophilic group and becomes a lipophilic nonionic surfactant having an AO site as lipophilic. When a = 0, a hydrophilic-lipophilic-hydrophilic triblock type nonionic surfactant having xylitol sites and EO sites on both sides of the AO site is obtained. Furthermore, when b = 0, the EO site functions to supplement the hydrophilicity of xylitol.

Thus, the nonionic surfactant of the present invention can take various molecular forms by appropriately selecting a + b and m, and can control hydrophilicity and lipophilicity according to the purpose. However, the case where a = b = 0, which acts as a lipophilic nonionic surfactant, is particularly preferred.
If EO is required to supplement hydrophilicity, a + b is 1 to 100, preferably 1 to 50, more preferably 1 to 30, still more preferably 1 to 20, and particularly preferably 1 to 10.

A and b are each 100 or less, preferably 50 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 10 or less. Moreover, although a and b may be 0, they may be 1 or more for the reasons described above. Particularly preferably, a is 0 to 10 and b = 0.

The ratio of the mass of (AO) m to the total mass of (EO) a, (EO) b, and (AO) m is 50 to 100 mass%. If this is less than 50% by mass, the lipophilicity may not be sufficient when used as an emulsifying solubilizer, which is not preferable. The amount is preferably 80 to 100% by mass, and more preferably 90 to 100% by mass.

R ¹ is a hydrogen atom, an alkyl having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and a mixed group thereof. It is a group. Examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, and the like. A hydrogen atom and an alkyl group having 1 to 4 carbon atoms are preferable, and a hydrogen atom, a methyl group, and an ethyl group are particularly preferable.

The xylitol site has four adjacent hydroxyl groups and acts as a hydrophilic group. The solid-liquid interface is essential as an adsorption site on the solid surface, and the liquid-liquid interface is essential as a hydrophilic group of the emulsification solubilizer.

In the case where there are two hydroxyl groups having a skeleton other than xylitol, for example, glycerin, or in the case where there are four hydroxyl groups as in the triglycerin derivative exemplified in cited reference 4 or 5, ether In the case of bonding, the adsorbing force on the solid surface is not sufficient. Therefore, in order to achieve the subject of this application, a xylitol site | part becomes essential.

[Production method of polyalkylene glycol derivative]
The polyalkylene glycol derivative represented by the general formula (1) can usually be produced by the following procedures (1) to (3).
(1) Xylitol is reacted with a ketalizing agent or acetalizing agent in the presence of an acid catalyst to obtain a xylitol diketal compound or diacetal compound represented by the following general formula (2).
The xylitol diketalized product or diacetalized product of formula (2) may be purified by distillation or the like, if necessary.

(2) Subsequently, an addition reaction of an oxyethylene group and an oxyalkylene group having 3 to 4 carbon atoms is carried out under an alkali catalyst, and if necessary, an alkyl halide, an acyl halide, an acid anhydride, etc. under an alkali catalyst. The terminal hydroxyl group can be etherified or esterified by reacting.
(3) Thereafter, deketalization or deacetalization is performed in the presence of an acid.

In the formula (2), R ² and R ³ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ do not simultaneously become a hydrogen atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and a methyl group and an ethyl group are preferable. When R ² = R ³ = methyl group, acetone and 2,2-dimethoxypropane can be exemplified as the ketalizing agent, and when R ² = hydrogen atom and R ³ = methyl group, acetaldehyde can be exemplified as the acetalizing agent. .

Examples of the ketalization or acetalization catalyst include acid catalysts such as sulfuric acid and paratoluenesulfonic acid. Usually, the charge amount of the ketalizing agent or acetalizing agent is 200 to 400 mol% with respect to xylitol, and the charge amount of the acid catalyst is 5 × 10 ⁻⁶ to 15 × 10 ⁻³ mol% with respect to xylitol. However, the reaction temperature is generally 30 to 90 ° C.

When the xylitol diacetalized product or diketalized product of formula (2) is used in the alkylene oxide addition reaction in the next step, there is no particular need to perform catalyst removal treatment, etc., but if necessary, neutralization treatment with alkali And acid adsorption treatment, filtration and the like. For example, neutralizing agents such as potassium hydroxide, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium acetate, Kyowa Chemical Industry Co., Ltd. Kyoward 300, Kyoward 500, Kyoward 1000, Kyoward 2000, Adsorbents such as Tomix AD-500 manufactured by Tomita Pharmaceutical Co., Ltd., and other zeolites can be used.

When the compound of formula (2) is subjected to an alkylene oxide addition reaction in the presence of an alkali catalyst, the reaction is usually performed at 40 to 180 ° C. in a pressure reaction kettle such as an autoclave. At this time, as the alkali catalyst, alkali metal or alkaline earth metal oxides, hydroxides, alcoholates and the like can be used. The amount of the catalyst used is not particularly limited, but is generally 0.01 to 5.0% by mass with respect to the mass after completion of the addition reaction.

If necessary, the compound of the formula (3) after the addition reaction of alkylene oxide can be reacted with an alkyl halide having 1 to 4 carbon atoms in the presence of an alkali to form an alkyl ether. Examples of alkyl halides include methyl chloride, ethyl chloride, propyl chloride, butyl chloride, methyl bromide, ethyl bromide, methyl iodide, ethyl iodide and the like. Moreover, as an alkali at this time, an alkali metal or alkaline earth metal oxide, hydroxide, alcoholate, or the like can be used. The amount of alkali halide charged is generally 100 to 400 mol% with respect to the number of hydroxyl groups to be reacted, the alkali amount is 100 to 500 mol% with respect to the number of hydroxyl groups to be reacted, and the reaction temperature is generally 60 to 180 ° C. It is.

For the compound of the formula (3), if necessary, in the presence of an alkali or acid catalyst, an acylating agent such as a carboxylic acid having 1 to 4 carbon atoms, a carboxylic acid halide, a carboxylic acid anhydride, It can also be esterified. Examples of carboxylic acids include acetic acid, propionic acid, butyric acid, etc. Examples of carboxylic acid halides include acetic acid chloride, propionic acid chloride, butyric acid chloride, and acid anhydrides include acetic anhydride, propionic anhydride, and the like. The amount of acylating agent charged is 100 to 400 mol% with respect to the number of hydroxyl groups to be reacted, the amount of alkali or acid catalyst is 0.01 to 500 mol% with respect to the number of hydroxyl groups to be reacted, and the reaction temperature is 60 to 180 ° C. It is common to do in.

The deketalization or deacetalization reaction in the oxyalkylenated compound of the compound of formula (3) is performed in the presence of an acid. Examples of the acid include hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, acetic acid, citric acid, succinic acid, tartaric acid, paratoluenesulfonic acid, other solid acids, cation exchange resins, and acid clay. The amount of the acid used is 0.001 to 6.0% by mass with respect to the oxyalkylenated product of the compound of formula (3). Further, if necessary, the reaction can be carried out by adding water, and the amount used is 0.01 to 100% by mass. The reaction temperature is generally 60 to 150 ° C.

After completion of the deketalization or deacetalization reaction, neutralization treatment with an alkali, acid adsorbent treatment, filtration, or the like can be performed. For example, neutralizers such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium acetate, Kyowa Chemical Industry Co., Ltd. Kyoward 300, Kyoward 500, Kyoward 1000, Kyoward 2000, Adsorbents such as Tomix AD-500 manufactured by Tomita Pharmaceutical Co., Ltd., and other zeolites can be used.

As described above, the polyalkylene glycol derivative represented by the general formula (1) protects the hydroxyl group of xylitol by diketalization or diacetalization in advance, and performs an oxyalkylenation reaction of the hydroxyl group in this state. After etherification / esterification, a series of steps of deprotection by deketalization or deacetalization reaction is performed. Thereby, a polyalkylene glycol derivative in which one hydroxyl group of xylitol is modified as shown in the formula (1) can be obtained.
The polyalkylene glycol derivative of the present invention is particularly good as an emulsifying solubilizing agent and dispersing agent, but the application is not limited thereto. Applications can be used for emulsifiers, solubilizers, dispersants, antifoaming agents, lubricants, penetrants, cleaning agents, and the like.

[Cosmetics]
The blending amount of the polyalkylene glycol derivative in the cosmetic of the present invention is not particularly limited, but is preferably 0.001 to 50% by mass, more preferably 0.01 to 30% by mass.

In the cosmetics of the present invention, various components generally used in cosmetics, pharmaceuticals and the like can be blended as needed, as long as the effects of the present invention are not impaired. For example, hydrocarbons, higher alcohols, higher fatty acids and their triglycerides, ester oils, animal and vegetable oils, silicones, vitamins, UV absorbers, water-soluble polymers, antioxidants, cationic surfactants, anionic interfaces Examples include activators, amphoteric surfactants, nonionic surfactants, sequestering agents, ethanol, thickeners, preservatives, dyes, pigments, and fragrances.

Moreover, the product form of the cosmetic comprising the polyalkylene glycol derivative of the present invention is not particularly limited, and W / O emulsion cosmetic, O / W emulsion cosmetic, W / O / W emulsion cosmetic. Any of cosmetics composed of a bicontinuous phase of oil and water, oily cosmetics and the like may be used, but it can be suitably used as a W / O emulsified cosmetic. In this case, the polyalkylene glycol derivative of the present invention acts as a W / O type emulsifier. In this case, the polyalkylene glycol derivative is preferably contained in an amount of 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total mass of the cosmetic.

In addition to the polyalkylene glycol derivative of the present invention, the cosmetic preferably contains 5 to 95% by mass of an oil agent, more preferably 10 to 90% by mass.

As oil agents that can be used in cosmetics, it is preferable to use hydrocarbon oils, higher alcohols, higher fatty acids, ester oils, triglycerides including fats and oils, and silicone oils in combination.

Hydrocarbon oils include liquid paraffin, polybutene, hydrogenated polyisobutene, hydrogenated polydecene, squalane, squalene, pristane, light isoparaffin, light liquid isoparaffin, heavy liquid isoparaffin, liquid isoparaffin, tetradecene, isohexadecane, isododecane, α-olefin. Examples include oligomers, petrolatum, microcrystalline wax, paraffin, polyethylene, and ceresin. Preferred are liquid paraffin, hydrogenated polyisobutene, squalane and petrolatum. One or more of these can be used.

The higher alcohol may be linear, branched, saturated or unsaturated. Such higher alcohols include octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, cetostearyl alcohol, isocetyl alcohol, stearyl alcohol, oleyl alcohol, isostearyl alcohol, aralkyl. Alcohol, behenyl alcohol, jojoba alcohol and the like can be exemplified by higher alcohols having 8 or more carbon atoms. These can be used alone or in combination of two or more.

The higher fatty acid may be any of linear, branched, saturated, unsaturated, and hydroxyl group-containing types. Such higher fatty acids include caprylic acid, capric acid, 2-ethylhexanoic acid, lauric acid, myristic acid, myristoleic acid, coconut oil fatty acid, beef tallow fatty acid, palm oil fatty acid, palmitic acid, palmitoleic acid, stearic acid And higher fatty acids having 8 or more carbon atoms such as oleic acid, isostearic acid, ricinoleic acid, linoleic acid, linolenic acid, arachidic acid, behenic acid, arachidonic acid and erucic acid. These can be used alone or in combination of two or more.

Ester oils include diethyl sebacate, cetyl 2-ethylhexanoate, isocetyl 2-ethylhexanoate, isopropyl palmitate, octyl palmitate, 2-ethylhexyl palmitate, isopropyl isostearate, 2-hexyldecyl isostearate, isostearic acid Isostearyl, trimethylolpropane triisostearate, octyldodecyl myristate, isopropyl myristate, isostearyl myristate, isocetyl myristate, hexyl laurate, ethyl oleate, decyl oleate, isostearyl pivalate, butyl stearate, stearin Octyl acid, stearyl stearate, isopropyl isostearate, isononyl isononanoate, 2-ethylhexyl isononanoate, Isodecyl sononanoate, isotridecyl isononanoate, octyldodecyl erucate, neopentyl glycol didecanoate, pentaerythrityl tetraethylhexanoate, diisostearyl malate, trimethylolpropane triethylhexanoate didecyl adipate, didecyl adipate (adipic acid 2-ethylhexanoic acid / stearic acid) glyceryl oligoester, glyceryl isostearate, isostearic acid hydrogenated castor oil, cholesteryl isostearate, batyl isostearate, phytosteryl isostearate, octyl oxystearate, glyceryl oleate, diglyceryl oleate, Dihydrocholesteryl oleate, phytosteryl oleate, coconut oil fatty acid pentaerythritol, stearic acid hardened Shear oil, diglyceryl stearate, soft lanolin fatty acid cholesteryl, hydroxy cholesteryl hydroxy stearate, dipentaerythritol hexaoxystearate, monohydroxystearic acid hydrogenated castor oil, lanolin fatty acid isostearyl, lanolin fatty acid isopropyl, lanolin fatty acid octyldodecyl, lanolin Examples include fatty acid cholesteryl, glyceryl ricinoleate, cetyl ricinoleate, and the like. One or more of these can be used.

Examples of triglycerides containing fats and oils include caproic acid, caprylic acid, capric acid, 2-ethylhexanoic acid, lauric acid, myristic acid, myristoleic acid, coconut oil fatty acid, beef tallow fatty acid, palm oil fatty acid, palmitic acid, palmitoleic acid, stearin Triglycerides of higher fatty acids having 6 or more carbon atoms such as acid, oleic acid, isostearic acid, linoleic acid, linolenic acid, arachidic acid, behenic acid, arachidonic acid, erucic acid, glyceryl trioxystearate, tri (Myristin stearic acid) glyceride, trilanolin fatty acid glyceryl, olive oil, corn oil, peanut oil, rapeseed oil, sesame oil, soybean oil, palm oil, palm oil, palm kernel oil, castor oil, flaxseed oil, jojoba oil, camellia oil, sunflower oil , Macadamia nut oil, Seed oil, cotton seed oil, perilla oil, Safuwara oil, apricot kernel oil, beef tallow, animal and vegetable fats and oils such as lard can be exemplified. One or more of these can be used.

Silicone oils include linear polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and tetrahydrotetramethylcyclotetrasiloxane. Examples thereof include cyclic polysiloxanes such as polyoxyethylene polyalkylsiloxane. One or more of these can be used.

Of these oils, hydrocarbon oils, ester oils, and silicone oils are particularly preferable.

For example, when used as a W / O type emulsified cosmetic, the polyalkylene glycol derivative of the present invention can stably disperse inorganic pigments. In this case, it is particularly preferable to use it as a cosmetic in which an inorganic pigment is stably dispersed in an oil phase composed of hydrocarbon oil and silicone oil.

That is, in this embodiment, an emulsified cosmetic (particularly preferably a W / O type cosmetic) comprising the composition of the following component (a), component (b), component (c), component (d) and component (e): ) Is preferred.
(A) Polyalkylene glycol derivative of formula (1) (b) Inorganic pigment (c) Hydrocarbon oil liquid at 25 ° C. (d) Silicone oil (e) Water

In the present embodiment, the component (a) is contained in an amount of 0.01 to 30% by mass (preferably 0.1 to 20% by mass), and the component (b) is contained in an amount of 0.1 to 50% by mass (preferably 1 to 50% by mass). %)contains. Further, the total of the component (c) and the component (d) is 10 to 95% by mass, and the component (e) is 5 to 80% by mass. Further, when the total amount of component (c) and component (d) is 100 parts by weight, the ratio of component (c) is 10 parts by mass or more (ratio of component (d) is 90 parts by mass or less), preferably The ratio of the component (c) is 90 parts by mass or less (the ratio of the component (d) is 10 parts by mass or more).

(B) The component is an inorganic pigment. For example, inorganic reds such as titanium oxide, zinc oxide, anhydrous silicic acid, aluminum silicate, magnesium silicate, calcium silicate, talc, mica, sericite, kaolin, bentonite, red iron oxide (Bengara), iron titanate, etc. Pigments, inorganic brown pigments such as γ-iron oxide, inorganic yellow pigments such as yellow iron oxide and ocher, inorganic black pigments such as black iron oxide and carbon black, inorganic purple pigments such as mango violet and cobalt violet, Examples thereof include inorganic green pigments such as chromium oxide, chromium hydroxide and cobalt titanate, inorganic blue pigments such as ultramarine and bitumen, and pearl pigments such as titanium oxide-coated mica, bismuth oxychloride and oxybismuth oxide-coated titanium oxide. One or more of these can be used. Preferred are titanium oxide, zinc oxide, anhydrous silicic acid, aluminum silicate, magnesium silicate, calcium silicate, talc, mica, sericite, kaolin and bentonite, and more preferred are titanium oxide and zinc oxide.

There are no particular restrictions on the shape (spherical, rod-like, plate-like, needle-like, etc.) and particle diameter of the inorganic pigment, but a particle diameter of 300 nm or less is common.

These inorganic pigments are known surface treatments such as fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, oil agent treatment, N-acylated lysine treatment, Surface treatment may be performed by acrylic acid treatment, metal soap treatment, amino acid treatment, lecithin treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment, or the like.

(C) Component is hydrocarbon oil which is liquid at 25 ° C. The hydrocarbon oil has an action of improving the compatibility between the polyalkylene glycol derivative represented by the formula (1) and the silicone oil of the component (d), and brings about dispersion stability.

The hydrocarbon oil which is liquid at 25 ° C. is not particularly limited, and liquid paraffin, polybutene, hydrogenated polyisobutene, hydrogenated polydecene, squalane, squalene, pristane, light isoparaffin, light liquid isoparaffin, heavy liquid isoparaffin, liquid isoparaffin, tetradecene, Examples thereof include isohexadecane, isododecane and α-olefin oligomer. One or more of these can be used. Preferred are liquid paraffin, hydrogenated polyisobutene, and squalane.

Component (d) is silicone oil, which is an essential component for improving smoothness when applied to skin and hair. Specifically, linear polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetrahydrotetramethylcyclotetrasiloxane Examples thereof include cyclic polysiloxanes such as polyoxyethylene polyalkylsiloxane, and one or more of these can be used. Cyclic polysiloxane is preferable.

The total amount of component (c) and component (d) is 10 to 95% by mass, particularly preferably 20 to 90% by mass, based on the total amount of the cosmetic. Further, when the total amount of the component (c) and the component (d) is 100 parts by weight, the amount of the component (c) is 10 parts by mass or more, preferably 20 parts by mass or more, more preferably 30 parts. More than part by mass. By making this 10 parts by mass or more, the above effect becomes remarkable. Further, when the total amount of the component (c) and the component (d) is 100 parts by weight, the amount of the component (c) is preferably 90 parts by weight or less, more preferably 80 parts by weight or less, and the effect is remarkable. Become.
The water of component (e) is not particularly limited as long as it is generally used as an aqueous phase of W / O emulsified cosmetics. For example, purified water such as distilled water or ion exchange water, physiological saline, phosphoric acid A citrate buffer aqueous solution or the like can be preferably used. In the present composition, the amount of water is 5 to 80% by mass, more preferably 10% by mass or more, and further preferably 75% by mass or less.

In addition, when the five components (a) to (e) are used as the composition and the total mass is set to 100 parts by mass, the preferable ranges of the parts by mass of the components (a) to (e) are as follows: It is.
Component (a): 0.01 to 30 parts by mass (more preferably 0.1 to 20 parts by mass)
Component (b): 0.1 to 50 parts by mass (more preferably 1 to 50 parts by mass)
Total amount of component (c) and component (d): 10 to 95 parts by mass (more preferably 15 to 90 parts by mass)
Component (e): 5 to 80 parts by mass (more preferably 10 to 80 parts by mass)

This cosmetic is preferably used as a sunscreen cosmetic such as a sunscreen lotion as a product form.
Furthermore, the form of the cosmetic of the present invention can take any form of liquid, semi-solid, or solid at room temperature, and other components can be contained within a range that does not impair the performance of the present invention. For example, lower alcohols, natural fats and oils, synthetic triglycerides, ester oils, waxes, oily bases, anionic surfactants, amphoteric surfactants, nonionic surfactants, cationic surfactants, semipolar Surfactants, water-soluble polymers, organic or inorganic salts, pH adjusters, bactericides, chelating agents, antioxidants, ultraviolet absorbers, vitamins, natural extracts derived from animals and plants, pigments, pigments, fragrances, etc. .

Moreover, the product form of the cosmetic comprising the polyalkylene glycol derivative of the present invention is not particularly limited to the aforementioned form, but is preferably a skin external preparation. Skin external preparations include skin care cosmetics such as lotions, emulsions, creams and packs; makeup cosmetics such as foundations, lipsticks and eye shadows; sunscreen cosmetics (sunscreen agents); body cosmetics; aromatic cosmetics Skin cosmetics such as make-up removers and body shampoos; hair cosmetics such as hair liquids, hair tonics, hair conditioners, hair shampoos, rinses, hair restorers; ointments and the like.

[Synthesis example]
The synthesis example of the polyalkylene glycol derivative concerning this invention is shown. The hydroxyl value was measured according to JISK1557 6.4.
Synthesis Example 1: Polyoxybutylene (40 mol) xylitol (Compound 1)
(1) Ketalization reaction A 3 liter four-necked flask equipped with a stirring blade, a nitrogen blowing tube, a thermocouple, a cooling tube and an oil-water separation tube was charged with 700 g of xylitol, 1291 g of 2,2-dimethoxypropane, and paratoluenesulfonic acid. Hydrate (27 mg) was charged, and the reaction system was maintained at 60 to 90 ° C. and reacted for 2 hours. After completion of the reaction, by-product methanol and excess 2,2-dimethoxypropane were removed to obtain 1014 g of diisopropylidenexylitol (compound 1a, R ² = R ³ = methyl group). The hydroxyl value was 240 KOHmg / g. A comparison of xylitol and IR chart of a compound 1a of the raw material, the compound 1a is smaller peak of hydroxyl group in the vicinity of 3500 cm ^-1, ^{2960 cm} -1 ^{instead, 2870cm ^-1, 1460cm ^-1, 1380cm} around ^-1 It was confirmed that the peak of.

(2) Oxybutylene reaction 235 g of compound 1a and 15.5 g of potassium hydroxide were charged into an autoclave, and the air in the autoclave was replaced with dry nitrogen, and then the catalyst was completely dissolved at 140 ° C. with stirring. Next, 2900 g of 1,2-butylene oxide was added dropwise by a dropping device and stirred for 2 hours. Thereafter, the reaction product is taken out from the autoclave, neutralized with hydrochloric acid to pH 6-7, and subjected to reduced pressure treatment at 100 ° C. for 1 hour to remove the contained water. Finally, the salt is filtered to remove the salt. Removal of 2850 g of polyoxybutylene (40 mol) diisopropylidene xylitol (compound 1b) was obtained. The hydroxyl value was 18.1 KOHmg / g.

(3) Deketalization reaction Into a 1 liter four-necked flask equipped with a stirring blade, a nitrogen blowing tube, a thermocouple, and a cooling tube were charged 700 g of Compound 1b, 70 g of water, and 10 g of 36% hydrochloric acid, and 80 in a sealed state. After the deketalization reaction at 2 ° C. for 2 hours, water and acetone were distilled out of the system by nitrogen bubbling. Subsequently, the solution was adjusted to pH 6 to 7 with a 10% aqueous potassium hydroxide solution and subjected to reduced pressure treatment at 100 ° C. for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt generated after the treatment, and 650 g of polyoxybutylene (40 mol) xylitol (Compound 1) was obtained.

In addition, when GPC analysis was performed about the compound 1 obtained by the above, the molecular weight of the main peak was 2989. The analysis conditions are as follows.
Analytical instrument: SHODEX GPC SYSTEM-11 (manufactured by Showa Denko)
Standard substance: Polyethylene glycol Sample size: 10% x 100 x 0.001 mL
Eluent: THF
Flow rate: 1.0 mL / min
Column: SHODEX KF804L (manufactured by Showa Denko)
Column size: I.D. D. 8mm x 30cm x 3
Column temperature: 40 ° C
Detector: RI x 8
Further, when the IR analysis of Compound 1b and Compound 1 was compared, the peak of the hydroxyl group in the vicinity of 3500 cm ⁻¹ was large in Compound 1, and it was confirmed that the target substance was obtained.

Synthesis Example 2: Polyoxyethylene (5 mol) Polyoxybutylene (40 mol) Xylitol (Compound 2)
In the procedure of Synthesis Example 1, the ketalization reaction was changed as follows, and synthesis was performed to obtain polyoxyethylene (5 mol) polyoxybutylene (40 mol) xylitol (Compound 2).
(1) Ketalization reaction 700 g of xylitol, 1050 g of acetone, and 10 mg of paratoluenesulfonic acid monohydrate were added to a 3 liter four-necked flask equipped with a stirring blade, a nitrogen blowing tube, a thermocouple, a cooling tube and an oil-water separation tube. The reaction system was charged at 60 to 90 ° C. and reacted for 4 hours. After completion of the reaction, by-product water and excess acetone were removed to obtain 1002 g of diisopropylidenexylitol (compound 1a, R ² = R ³ = methyl group). The hydroxyl value was 235 KOH mg / g. A comparison of xylitol and IR chart of a compound 1a of the raw material, the compound 1a is smaller peak of hydroxyl group in the vicinity of 3500 cm ^-1, ^{2960 cm} -1 ^{instead, 2870cm ^-1, 1460cm ^-1, 1380cm} around ^-1 It was confirmed that the peak of.

(2) Oxyethylene and oxybutylene reaction 235 g of compound 1a and 20 g of potassium hydroxide were charged into an autoclave, and the air in the autoclave was replaced with dry nitrogen, and then the catalyst was completely dissolved at 140 ° C. with stirring. Next, 230 g of ethylene oxide was dropped with a dropping device and stirred for 2 hours. Subsequently, 2900 g of 1,2-butylene oxide was added dropwise and stirred for 2 hours. Thereafter, the reaction product is taken out from the autoclave, neutralized with hydrochloric acid to pH 6-7, and subjected to reduced pressure treatment at 100 ° C. for 1 hour to remove the contained water. Finally, the salt is filtered to remove the salt. Removal gave 3028 g of polyoxyethylene (5 mol) polyoxybutylene (40 mol) diisopropylidene xylitol (compound 2b). The hydroxyl value was 17.0 mgKOH / g.

(3) Ketalization reaction 700 g of compound 2b, 70 g of water, and 10 g of 36% hydrochloric acid were charged in a 1-liter four-necked flask equipped with a stirring blade, a nitrogen blowing tube, a thermocouple, and a cooling tube, and sealed at 80 ° C. After performing the deketalization reaction for 2 hours, water and acetone were distilled out of the system by nitrogen bubbling. Subsequently, the solution was adjusted to pH 6 to 7 with a 10% aqueous potassium hydroxide solution and subjected to reduced pressure treatment at 100 ° C. for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt produced after the treatment, and 670 g of polyoxyethylene (5 mol) polyoxybutylene (40 mol) xylitol (compound 2) was obtained.

When GPC analysis was performed according to Synthesis Example 1, the molecular weight of the main peak was 3121. Further, when the IR analysis of Compound 2b and Compound 2 was compared, the peak of the hydroxyl group in the vicinity of 3500 cm ⁻¹ was large in Compound 1, confirming that the target substance was obtained.

The present inventors prepared polyalkylene glycol derivatives having the compositions shown in Table 1 below in accordance with Synthesis Examples 1 and 2 above.

<Evaluation of dispersibility>
[Preparation method]
1.0 g of titanium oxide and 1.0 g of a dispersant such as a polyalkylene glycol derivative were weighed and made into a total amount of 40 g using liquid paraffin (Moleco White P-70 manufactured by Moresco) (2.5% titanium oxide solution). This was stirred with a disper (25 ° C., 5000 rpm × 3 min) and then allowed to stand at 40 ° C. for 1 week. The supernatant of this dispersion was collected, and a solution diluted 100 times with liquid paraffin was used as a sample solution.

[Transparency measurement]
The absorbance of the obtained diluted solution was measured at 300 nm. The results are shown in Table 2 and FIG.

<Evaluation of emulsion stability>
[Preparation method]
Liquid paraffin 30.0% by mass
Emulsifier 5.0% by mass
Water 65.0% by mass
Liquid paraffin (Molesco White P-70 manufactured by Moresco) and an emulsifier were uniformly stirred at 70 ° C., and water was slowly added at the same temperature to be preliminarily dissolved. This was stirred with a homomixer (5000 rpm × 5 minutes) to obtain a W / O type emulsifier composition.

[Evaluation criteria]
The emulsified state of the prepared emulsifier composition was judged visually by the following criteria immediately after emulsification and after storage at 40 ° C. for 1 month. The results are shown in Table 4.
○: Stable emulsion state.
X: A state in which oil floating is slightly observed.
XX: completely creamed or separated.

(Example 11)
A W / O type emulsion was prepared using the polyalkylene glycol derivative of the present invention. Of the base comprising the following composition, the oil phase and the water phase were each dissolved by heating at 70 ° C. to dissolve uniformly, and then the water phase was slowly added to the oil phase while stirring to the room temperature. Until cooled.

Oil phase:
Liquid paraffin 25.0% by mass
Lanolin 2.0% by mass
Beeswax 2.0% by mass
Hydrogenated polyisobutene 20.0% by mass
Compound 1 5.0% by mass
Perfume Appropriate amount Preservative Appropriate amount Aqueous phase:
Glycerin 5.0% by mass
Water balance

(Comparative Example 15)
A W / O type emulsion having the following composition was prepared in the same manner as in Example 11.
Oil phase:
Liquid paraffin 25.0% by mass
Lanolin 2.0% by mass
Beeswax 2.0% by mass
Hydrogenated polyisobutene 20.0% by mass
Compound 6 5.0 mass%
Perfume Appropriate amount Preservative Appropriate amount Aqueous phase:
Glycerin 5.0% by mass
Water balance

(Example 12)
An O / W type skin cream was prepared using the polyalkylene glycol derivative of the present invention. After heating and dissolving the oil phase and the aqueous phase at 70 ° C. in a base composed of the following composition uniformly, the oil phase is slowly added to the water phase while stirring and the mixture is allowed to reach room temperature. Cooled down.
Oil phase:
Liquid paraffin 10.0% by mass
Vaseline 3.0% by mass
Compound 4 5.0% by mass
Perfume appropriate amount Preservative appropriate amount Aqueous phase:
Glycerin 5.0% by mass
PEG # 4000 5.0 mass%
Water balance

(Comparative Example 16)
An O / W type skin cream having the following composition was prepared in the same manner as in Example 12.
Oil phase:
Liquid paraffin 10.0% by mass
Vaseline 3.0% by mass
Compound 7 5.0 mass%
Perfume Appropriate amount Preservative Appropriate amount Aqueous phase:
Glycerin 5.0% by mass
PEG # 4000 5.0 mass%
Water balance

(Example 13)
A W / O type emulsion was prepared using the polyalkylene glycol derivative of the present invention. After heating and dissolving the oil phase and the water phase at 70 ° C. in a base comprising the following composition uniformly, the water phase is slowly added to the oil phase while stirring, until the temperature reaches room temperature. Cooled down.
Oil phase:
2-ethylhexyl palmitate 20.0% by mass
Liquid paraffin 30.0% by mass
Lanolin 1.0% by mass
Beeswax 0.5 mass Compound 1 3.0 mass%
Polyoxyethylene (20 mol) sorbitan monooleate 2.0% by mass
Perfume Appropriate amount Preservative Appropriate amount Aqueous phase:
Glycerin 4.0% by mass
1,3-butanediol 1.0% by mass
Water balance

(Comparative Example 17)
A W / O type emulsion having the following composition was prepared in the same manner as in Example 13.
Oil phase:
2-ethylhexyl palmitate 20.0% by mass
Liquid paraffin 30.0% by mass
Lanolin 1.0% by mass
Beeswax 0.5 mass Compound 6 3.0 mass%
Polyoxyethylene (20 mol) sorbitan monooleate 2.0% by mass
Perfume Appropriate amount Preservative Appropriate amount Aqueous phase:
Glycerin 4.0% by mass
1,3-butanediol 1.0% by mass
Water balance

For Examples 11, 12, 13 and Comparative Examples 15, 16, and 17, the emulsified state immediately after emulsification and after storage for 1 month at 40 ° C. was judged visually according to the following criteria. The results are shown in Table 5.
○: Stable emulsion state.
X: A state in which oil floating is slightly observed.
XX: completely creamed or separated.

(Example 14)
A cosmetic (sunscreen lotion) of the present invention was prepared. In the following composition, the A phase was mixed at room temperature, the B phase and the C phase were dissolved at room temperature, respectively, and then the B phase and the C phase were added to the A phase while stirring to emulsify.
Hereinafter, the content of the components is described as mass%, but the parts by weight of each component when the total amount of the components (a) to (e) is 100 parts by weight are also described. The same applies to Comparative Example 18.
Phase A:
Compound 1 (a) component 2.0 mass% (2.4 weight part)
Titanium oxide (b) component 10.0% by mass (12.1 parts by weight)
Zinc oxide (b) component 10.0% by mass (12.1 parts by weight)
Decamethylcyclopentasiloxane (c) component 10.0% by mass (12.1 parts by weight)
Squalane (d) component 3.0 mass% (3.6 parts by weight)
Octyldodecyl myristate 5.0% by mass
Polyoxyethylene (75 mol) monostearate
0.5% by mass
Polyoxyethylene (20 mol) sorbitan monostearate 0.5% by mass
Ethylhexyl methoxycinnamate 5.0% by mass
Phase B:
Butylene glycol 5.0% by mass
Water (e) Component 47.5% by mass (57.7 parts by weight)
Phase C:
Ethanol 1.0% by mass
Preservative appropriate amount Fragrance proper amount

(Comparative Example 18)
A sunscreen lotion having the following composition was prepared in the same manner as in Example 14.
Phase A:
Compound 6 2.0 mass% (2.4 parts by weight)
Titanium oxide (b) component 10.0% by mass (12.1 parts by weight)
Zinc oxide (b) component 10.0% by mass (12.1 parts by weight)
Decamethylcyclopentasiloxane (c) component 10.0% by mass (12.1 parts by weight)
Squalane (d) component 3.0 mass% (3.6 parts by weight)
Octyldodecyl myristate 5.0% by mass
Polyoxyethylene (75 mol) monostearate 0.5% by mass
Polyoxyethylene (20 mol) sorbitan monostearate 0.5% by mass
Ethylhexyl methoxycinnamate 5.0% by mass
Phase B:
Butylene glycol 5.0% by mass
Water (e) Component 47.5% by mass (57.7 parts by weight)
Phase C:
Ethanol 1.0 mass% (1.2 parts by weight)
Preservative appropriate amount Fragrance proper amount

Furthermore, according to Example 14, cosmetics (sunscreen lotions) of Examples 15 to 20 and Comparative Examples 19 to 23 were prepared. Table 6 shows. The emulsified state immediately after emulsification and after storage for 1 month at 40 ° C. was judged visually according to the following criteria. The results are also shown in Table 6.
○: Stable emulsion state.
X: Precipitate or phase separation is observed.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on February 1, 2010 (Japanese Patent Application No. 2010-019955) and a Japanese patent application filed on February 1, 2010 (Japanese Patent Application No. 2010-020008). Is incorporated herein by reference.

Claims

Polyalkylene glycol derivatives represented by the following general formula (1)

In the formula, EO is an oxyethylene group, AO is an oxyalkylene group having 3 to 4 carbon atoms, and EO and AO are bonded in a block form. The plurality of AOs may be the same as or different from each other.
a and b are the average addition moles of EO, m is the average addition moles of AO, a + b is 0 to 100, m is 10 to 100, (EO) a and (EO) b The ratio of the mass of (AO) m to the total mass of (AO) m is 50 to 100 mass%.
R 1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group having 1 to 4 carbon atoms.
The polyalkylene glycol derivative according to claim 1, wherein AO is an oxybutylene group derived from 1,2-butylene oxide.
In the polyalkylene glycol derivative represented by the formula (1), b = 0, and the ratio of the mass of (AO) m to the total mass of (EO) a and (AO) m is 80 to 100% by mass. The polyalkylene glycol derivative according to claim 1 or 2, characterized in that
Cosmetics containing the polyalkylene glycol derivative according to any one of claims 1 to 3.
Contains 0.01 to 30% by mass of the following component (a), 0.1 to 50% by mass of component (b), 5 to 80% by mass of component (c), component (d), and component (e) The total amount of the component (c) and the component (d) is 10 to 95% by mass, and the total amount of the component (c) and the component (d) is 100 parts by mass. 5. The cosmetic according to claim 4, wherein the amount of the component (c) is 10 parts by mass or more.
(A) Polyalkylene glycol derivative (b) Inorganic pigment (c) Hydrocarbon oil liquid at 25 ° C. (d) Silicone oil (e) Water